CN106715376A - Method of producing iridium complex - Google Patents
Method of producing iridium complex Download PDFInfo
- Publication number
- CN106715376A CN106715376A CN201580050429.4A CN201580050429A CN106715376A CN 106715376 A CN106715376 A CN 106715376A CN 201580050429 A CN201580050429 A CN 201580050429A CN 106715376 A CN106715376 A CN 106715376A
- Authority
- CN
- China
- Prior art keywords
- iridium
- beta
- solution
- acid
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 104
- 239000003513 alkali Substances 0.000 claims abstract description 83
- 238000010306 acid treatment Methods 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims description 68
- 238000001994 activation Methods 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 90
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000004913 activation Effects 0.000 abstract description 10
- 150000002504 iridium compounds Chemical class 0.000 abstract 4
- 239000007983 Tris buffer Substances 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- -1 fluorine Hydrogen Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 9
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical class CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- GWZHWRVINLCSIC-UHFFFAOYSA-N [Ir].[N+](=O)(O)[O-] Chemical compound [Ir].[N+](=O)(O)[O-] GWZHWRVINLCSIC-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 150000002503 iridium Chemical class 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005594 diketone group Chemical group 0.000 description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CVZIHXRHSDYALS-UHFFFAOYSA-N 1-fluoropentane-2,4-dione Chemical class CC(=O)CC(=O)CF CVZIHXRHSDYALS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 150000005360 2-phenylpyridines Chemical class 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- YESAPVFTAYLNBZ-UHFFFAOYSA-N [Ir].S(O)(O)(=O)=O Chemical compound [Ir].S(O)(O)(=O)=O YESAPVFTAYLNBZ-UHFFFAOYSA-N 0.000 description 1
- NRHLWEDJRGAWIA-UHFFFAOYSA-N [O-][N+]([O-])=O.[Ir+3] Chemical compound [O-][N+]([O-])=O.[Ir+3] NRHLWEDJRGAWIA-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PHHYVYYBYXVXHH-UHFFFAOYSA-K iridium(3+) triiodate Chemical compound [Ir+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] PHHYVYYBYXVXHH-UHFFFAOYSA-K 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A method of producing a tris ([beta]-diketonato) iridium, in which [beta]-diketone is made reacted with an iridium compound, is characterized in that the iridium compound is subjected to an activation treatment to thereby activate the iridium compound, and then react the [beta]-diketone. The activation treatment includes: (a) an alkali treatment where an alkali is added to a solution of the iridium compound to adjust a pH of the solution closer to an alkali side than that of pre-addition of alkali and pH 10 or higher; and (b) an acid treatment where an acid is added to the alkali-treated solution to adjust a pH of the solution closer to an acid side than that of pre-addition of acid and simultaneously pH difference to fall within 0.1-10. The method allows, when a tris ([beta]-diketonato) iridium is produced, a synthetic reaction to advance with no range of the [beta]-diketone to be coordinated to the iridium limited.
Description
Technical field
The present invention relates to a kind of method that three (beta-diketons) for manufacturing the complex of iridium for being coordinated in iridium as beta-diketon close iridium.
Specifically, it is related to a kind of method that broad category of beta-diketon can be made to be coordinated in iridium and synthesize complex of iridium.
Background technology
Three (beta-diketons) the conjunction iridium that beta-diketon is coordinated in iridium is known as in CVD (chemical vapor coating method), ALD
Starting compound (precursor) used in the chemical vapor deposition method of (atomic layer vapour deposition method) etc.For example, in patent document 1,2
Record a kind of starting compound of chemical vapor deposition, its be used to being formed by as complex of iridium three (5- methyl -2,4- oneself two
Ketone) close the iridium film that iridium or three (2,4- acetyl caproyls) conjunction iridium are constituted.
In addition, in recent years, parts of nibbling are studied more and the cyclometalated iridium complexes of iridium have been located at as organic using cyclic ligand
The application of the phosphor material of organic illuminating element such as galvanoluminescence (EL) element or luminous (ECL) element of organic electrochemistry is (specially
Sharp document 3).And, three (beta-diketons) close iridium and also are used as manufacturing the organic illuminating elements such as the cyclometalated iridium complexes
The raw material (intermediate raw material) of phosphor material.For example, having disclosed in non-patent literature 1:By with three (2,4- pentanediones)
Close iridium to be raw material and make it heteroaromatic 2 nibbles ligand reaction with 2- phenylpyridines (ppy) etc., and manufacture by Cyclometalated iridium structure
Into organic illuminating element phosphor material method.
Here, closing the manufacture method of iridium as three (beta-diketons), it is known to the iridium salt such as iridous chloride as initiation material, to
The beta-diketon of part is wherein added to, and adds saleratus etc. as alkalescence so as to the operation (patent document for being reacted
4)。
The existing synthetic method can be directly synthesized that above-mentioned three (5- methyl -2,4- acetyl butyryls) close iridium or three (2,4- is pungent
Diketone) close iridium, three (2,4- pentanediones) conjunction iridium.But, to be studied according to the present inventor etc., it is broad range of that confirmation will manufacture coordination
During the complex of iridium of beta-diketon, reaction is difficult to existing synthetic method.
For example, on the cyclometalated iridium complexes as above-mentioned phosphor material, it is necessary to rising to luminous efficiency
Target and to coordination have various parts complex study.In order to the starting for obtaining this cyclometalated iridium complexes is former
Material, present inventor etc. have attempted the synthesis of the complex of iridium of the following beta-diketon of coordination:The beta-diketon has such comprising fluorine
Hydrogen, carbon beyond element or cyclic hydrocarbon etc. various structures, but entering for synthetic reaction is cannot see that in existing method
Go and target three (beta-diketon) can not be obtained and close iridium.
Prior art literature
Patent document
Patent document 1:No. 4054215 specification of patent
Patent document 2:No. 4856825 specification of patent
Patent document 3:JP 2012-6914 publications
Patent document 4:Unexamined Patent 7-316176 publications
Non-patent literature
Non-patent literature 1:Inorg.Chem., volume 30, page 1685,1991
The content of the invention
Invent problem to be solved
Therefore, the present invention provides the manufacture method that iridium is closed for three (beta-diketons), can not limit the β that is coordinated-
The method for carrying out synthetic reaction in the case of the scope of diketone.
Technical scheme for solving problem
Problem in the present invention is characterized by, in general synthetic method, iridic compound relative to certain limit outside β-
The reactivity of diketone is it may be said that be almost wholly absent.For the problem, the present inventor etc. has made intensive studies, and as a result finds,
Iridic compound is activated by the activation process specified to the iridic compound as initiation material, even if so that phase
Also manifest reactivity for above-mentioned beta-diketon, target three (beta-diketon) can be synthesized and close iridium.
That is, the present invention closes the manufacture method of iridium for a kind of three (beta-diketons), and it is by making the beta-diketon shown in chemical formula 1
Reacted with iridic compound and manufacture the beta-diketon and be coordinated in the method that three (beta-diketons) shown in the chemical formula 2 of iridium close iridium, its
Be characterised by, carry out the activation process comprising following (a) alkali process and (b) acid treatment to the iridic compound and by iridium
After compound activation, then reacted with beta-diketon.
(a) alkali process:Alkali is added in the solution of the iridic compound, is in a ratio of before making the pH of solution and adding more alkaline
Side, and make the treatment that pH is more than 10.
(b) acid treatment:Acid is added in the solution for carried out the alkali process so that before the pH of solution is added with acid
More acidic side is in a ratio of, and the pH of the solution before and after acid addition is differed from the treatment for turning into less than more than 0.1 10.
[chemical formula 1]
(in formula, RaAnd RbFor the substitution base that the hydrogen atom of alkyl or alkyl is replaced by halogen atom.RaAnd RbIt can be difference
Substitution base, or identical replace base.RcIt is the substitution base being made up of any one of hydrogen atom, halogen atom, alkyl.)
[chemical formula 2]
(the R in formulaa、Rb、RcMeaning it is identical with chemical formula 1.)
Hereinafter, for the manufacture method of complex of iridium of the invention (three (beta-diketons) close iridium), each operation is explained
Content.
As the iridic compound for being used as initiation material in the present invention, can be with widely used iridic compound.For example can be with
Using the nitrate of iridium, sulfate, hydroxide, halide etc..More specifically, can apply:Nitric acid iridium, sulfuric acid iridium, hydrogen
Yttrium oxide, six ammonium chloroiridates, iridium chloride, iridium chloride acid, iridium chloride acid potassium, iridium chloride acid sodium, bromination iridium, the acid of bromination iridium, bromination
Iridium acid potassium, bromination iridium acid sodium, iodate iridium, yttrium oxide etc..The valence mumber of the iridium of these iridic compounds can be trivalent, or 4
Valency.
But, it is considered to when final three (beta-diketons) close the yield of iridium, preferred iridic compound be nitric acid iridium (III, IV),
Iridium chloride (III, IV), six ammonium chloroiridates (III, IV).In these iridic compounds, iridium is weaker with the bonding of anion.Entering
Row three (beta-diketon) close iridium synthetic reaction when, it is necessary to carry out as the iridic compound of initiation material decomposition and carry out by β-two
Ketone is converted into both conjugate bases of deprotonation, therefore, it can effectively be closed by the above-mentioned preferred iridic compound of application
Into complex.
Iridic compound is in the state of solution for reaction.As the solvent of iridic compound solution, preferably water.As solution
Iridic compound concentration, be preferably set to more than 0.01mol/L below 20mol/L.In addition, the pH of the solution of the iridic compound is most
More than 0 in less than 12 scope.
And, in the present invention, the solution to above-mentioned iridic compound is carried out at the activation comprising alkali process and acid treatment
Reason.These treatment have the effect of the state for making iridic compound be activation and the synthetic reaction for carrying out three (beta-diketons) conjunction iridium.
Alkali process are to add alkali in the solution of iridic compound, are in a ratio of more alkaline side before making its pH and alkali addition, and make
PH is more than 10 treatment.Alkali process more preferably make the pH of the solution of iridic compound be more than 12.The preferred hydrogen of alkali for now adding
Sodium oxide molybdena, potassium hydroxide, lithium hydroxide, cesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus,
Ammonia, TMAH.Alkali is preferably added with solution state, and the concentration of aqueous slkali is preferably set to more than 0.01mol/L
Below 20mol/L.The solution of the iridic compound on carrying out alkali process, preferably in the range of above-mentioned pH stand 0.5 hour with
After upper 24 hour is following, following treatment (acid treatment) is carried out.In addition, in alkali process, turning the pH of the solution of iridic compound
Move to the pH differences before and after the addition of the alkali in alkaline side, but the treatment and be preferably set to less than more than 2 13, more preferably set more than 5 13
Following pH is poor.
The acid treatment that alkali process are followed by carried out is that acid is added in the solution of the iridic compound of basic region, makes pH with acid
More acidic side is in a ratio of before addition and the treatment that front and rear pH differences are set to less than more than 0.1 10 is added into acid.The acid added herein
Preferably nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, cross chloric acid, phosphoric acid, sulfuric acid, hexafluoro-antimonic acid, four
Fluoboric acid, hexafluorophosphoric acid, chromic acid, boric acid, methanesulfonic acid, ethyl sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, trifluoromethayl sulfonic acid, acetic acid,
Citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid.The acid concentration of the acid solution of addition is preferably set to more than 0.01mol/L
Below 20mol/L.In addition, the pH differences before and after the acid in the acid treatment is added are preferably set to less than more than 1 10.
Iridic compound is activated by the activation process comprising alkali process and acid treatment described above.The iridic compound
Activation be revealed in and have been carried out alkali process and the stage both acid treatment.In addition, alkali process and the order of acid treatment are for first
Carry out alkali process.And, alkali process and acid treatment can be carried out at room temperature.Specifically, activation process can 0 DEG C with
Upper less than 50 DEG C are carried out.
Iridic compound after making activation process reacts with beta-diketon and carries out complex synthesis.Reacted herein
Beta-diketon is the beta-diketon of the iridium for being coordinated in manufacturing objective complex of iridium, i.e., the beta-diketon shown in the formula of above-mentioned chemical formula 1.
The R of the beta-diketon in the formula of chemical formula 1aAnd RbFor the substitution base that the hydrogen atom of alkyl or alkyl is replaced by halogen atom.
RaAnd/or RbDuring for alkyl, preferably aliphatic alkyl or aromatic hydrocarbyl.In addition, the hydrogen atom of these alkyl is it is also preferred that by halogen
Atom replaces.
More specifically, RaAnd/or RbDuring for aliphatic alkyl, the preferably alkyl of straight-chain or branched.In addition, excellent
Select the aliphatic alkyl of carbon number 1~10.Can enumerate for example:Alkyl (more preferably carbon number 1~5), cycloalkyl, neopentyl.More
For body, can enumerate:Methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, ring
Propyl group, cyclopenta, cyclohexyl, neopentyl etc..And, the hydrogen atom in these aliphatic alkyls by fluorine it is also preferred that replaced.In addition,
RaAnd RbCan be different substitution bases, or identical replaces base.
RaAnd/or RbDuring for aromatic hydrocarbyl, the preferred aromatic hydrocarbyl of carbon number 6~20.More preferably carbon number 6~10
Aromatic hydrocarbyl.Specifically, have:Phenyl, naphthyl, xenyl, fluorenyl, phenanthryl, anthryl, Sanya phenyl, terphenyl, pyrene
Base, mesitylene base, tolyl, xylyl, azulenyl, acenaphthenyl, indenyl etc..And, the hydrogen atom in these aromatic hydrocarbyls
It is also preferred that being replaced by fluorine.In addition, RaAnd RbCan be different substitution bases, or identical replaces base.
In addition, RcIt is the substitution base being made up of any one of hydrogen atom, halogen atom, alkyl.RcSubstitution base be halogen atom
When, particularly preferably fluorine atom.RcDuring for alkyl, the preferably alkyl of straight-chain or branched.Additionally, it is preferred that for carbon number 1~
10 aliphatic alkyl.Can enumerate for example:Alkyl (more preferably carbon number 1~5), cycloalkyl, neopentyl.More specifically, may be used
Enumerate:Methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, n-octyl, positive decyl, n-hexadecyl, cyclopropyl, ring penta
Base, cyclohexyl, neopentyl etc..And, the hydrogen atom in these aliphatic alkyls by fluorine it is also preferred that replaced.
As the concrete example of the beta-diketon for considering above-mentioned situation, can react beta-diketon as described below.
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
Incidentally, it is in iridium chemical combination as the specific operation for reacting the iridic compound of activation and beta-diketon
Beta-diketon is added in thing solution.As the opportunity that the beta-diketon is made an addition to iridic compound solution, can terminate in activation process
Add beta-diketon in iridic compound solution afterwards, it is also possible to before activation process terminates in iridic compound solution add β-two
Ketone, then carries out activation process.
When adding beta-diketon in the iridic compound solution after activation process terminates, can be straight by the solution after activation process
Connect for synthetic reaction.But the species of starting compound is sometimes depended on, precipitate can be produced because of activation process.The situation
Under, can filter and reclaim precipitate and be dispersed in water it, and be added to beta-diketon.And, by activation
Solution after reason adds beta-diketon in the dispersion soln of precipitate, so as to carry out the synthetic reaction that three (beta-diketons) close iridium.
On the other hand, as the technical meaning of the addition beta-diketon in the iridic compound solution before activation process terminates, bag
Include following two situations:Adding beta-diketon before carrying out both alkali process and acid treatment in iridic compound solution in advance
Situation, and be added in the midway stage of activation process, i.e. in the centre of alkali process and acid treatment in iridic compound solution
Add the situation of beta-diketon.
When beta-diketon is added in the iridic compound solution before activation process terminates, do not enter in the addition stage of beta-diketon
Row three (beta-diketon) closes the synthetic reaction of iridium.Start synthetic reaction by terminating the acid treatment of activation process.
As described above, being allowed for reason as 3 kinds of patterns of the mode that beta-diketon is made an addition to iridic compound solution, it is
Because, in order that the synthetic reaction that three (beta-diketons) close iridium is carried out, it is necessary to activate iridic compound, and iridic compound activation
Manifested by the end of both alkali process and acid treatment.
Additionally, it is contemplated that during addition opportunity of 3 kinds of beta-diketons as described above, add as the alkali in activation process, acid
" solution before alkali (acid) addition " of the benchmark of the pH adjustment of added-time refers to the solution before the addition alkali (acid) as shown in word
Meaning.That is, when beta-diketon is added after the activation process of iridic compound terminates, " solution " before alkali addition is that iridic compound is molten
Liquid.On the other hand, when adding beta-diketon in iridic compound solution in advance before activation process (alkali process) is carried out, alkali addition
Preceding " solution " is the mixed solution of iridic compound solution and beta-diketon.In addition, in alkali process and the intermediate step of acid treatment
When adding beta-diketon in iridic compound solution, " solution " before alkali addition is only iridic compound solution, but " molten before acid addition
Liquid " is the mixed solution of iridic compound solution and beta-diketon.
And, when adding beta-diketon in iridic compound solution, depending on its species, the pH of iridic compound solution can change
(not changing mostly).When the mixed solution of iridic compound solution and beta-diketon is equivalent to solution before above-mentioned alkali (acid) addition,
The pH of the solution uses the value of the state of mixed solution.In addition, being applied equally to add and calculate by above-mentioned alkali (acid)
Preferred pH difference benchmark.
And, the reaction condition on iridic compound and beta-diketon, the addition of beta-diketon is than manufacturing objective complex of iridium
Equivalents (relative to iridium be 3 equivalents) more.Below more than iridium 3 equivalents of addition 20 equivalents.
Terminate on activation process and the iridic compound solution containing beta-diketon, in order to be more effectively carried out three (beta-diketons)
The synthetic reaction of iridium is closed, solution can be heated.Activation process can be carried out at room temperature, but by be heated to room temperature with
On temperature, can improve three (beta-diketons) close iridium synthetic reaction yield.As reaction temperature now, it is preferably kept at
Less than more than 50 DEG C 100 DEG C.Reaction time is preferably set to less than 24 hours more than 0.5 hour.
The complex of iridium of generation is precipitated with reaction solution after complex synthetic reaction.Carried out separation of solid and liquid simultaneously clear
Wash after solid constituent, refined, it is hereby achieved that three (beta-diketons) of high-purity close iridium.
Invention effect
As described above, the manufacture method of three (beta-diketons) conjunction iridium of the invention can make broad category of β-two
Ketone is coordinated in iridium.Thus, it is possible to expand the possibility that three (beta-diketons) of the manufacture with multifrequency nature close iridium, as developing
It is suitable as the basis of the material of phosphor material or film the formation raw material of organic electrolysis light-emitting component etc..
Specific embodiment
Below, preferred embodiment illustrated to of the invention.As described above, being closed in of the invention three (beta-diketons)
In the manufacture method of iridium, the opportunity of beta-diketon is added as the solution to iridic compound, there are following Three models:(1) in activation
Treatment terminate after iridic compound solution in add beta-diketon method;(2) before both alkali process and acid treatment is carried out
The method for adding beta-diketon in iridic compound solution in advance;(3) in the midway (centre of alkali process and acid treatment of activation process
Stage) method of addition beta-diketon in iridic compound solution.In the present embodiment, the operation manufacture based on (1)~(3)
Complex of iridium.
1st implementation method:In the present embodiment, complex of iridium is manufactured by the operation of above-mentioned (1).In this as starting
The iridic compound of raw material, uses nitric acid iridium (III) Ir (NO3)3, make it with 1,1,1,6,6,6- hexafluoro -2 as beta-diketon, 4-
Pentanedione (alias:Hexafluoroacetylacetone) reaction, manufacture three (1,1,1,6,6,6- hexafluoro -2,4- pentanediones) conjunction iridium (three (hexafluoros
Acetylacetone,2,4-pentanedione) close iridium).
[chemical formula 7]
Prepare concentration 9.1wt% in 20.26g nitric acid iridium (iridium content 1.84g, 9.6mmol)) in addition 18.8mL distillations
Nitric acid iridium solution obtained by water.The nitric acid iridium solution is the navy blue aqueous solution, and pH is 0.7.
Alkali process for activation process and acid treatment are carried out to the nitric acid iridium solution.In alkali process, the hydrogen of 1N is added
Sodium hydroxide solution.In alkali process, make the pH (0.7) of the nitric acid iridium solution before being added relative to alkali as alkaline side.In this reality
In applying mode, adjust alkali addition and become the solution of different pH.After alkali addition, nitric acid iridium solution is stood at room temperature
1 hour.
Afterwards, as acid treatment in the solution, 6% dust technology is added.Acid treatment is formed also by the sour addition of adjustment
It is different pH.In addition, being navy blue in the solution in appearance without big change in alkali process and acid treatment more than
The aqueous solution.
In the nitric acid iridium solution for carrying out above-mentioned alkali process and acid treatment and terminating activation process add 19.5g,
1,1,1,6,6,6- hexafluoro -2,4- the pentanediones of 59.2mmol.The addition is relative to 1mol iridium equivalent to 6 equivalents.1,1,1,
6,6,6- hexafluoro -2, after the addition of 4- pentanediones, 55 DEG C are heated to by solution, are kept for 2.5 hours and are reacted it.
Reacted reaction solution turns into the suspension of dark yellow.The pH of reaction solution is slightly biased to acidic side.By the reaction solution
Separation of solid and liquid is filtered and carried out, after cleaning solid constituent, the refined (solvent of post is carried out;Hexane:Ethyl acetate=5:1) reclaim
Three (1,1,1,6,6,6- hexafluoro -2,4- pentanediones) close iridium.
To synthesis, the complex of iridium for reclaiming, parsed by 1H NMR (proton magnetic resonance (PMR)) and x-ray structure and divided
Analysis.Here, 1H NMR are analyzed by 1H NMR devices (400MHz), measure solvent C DCl is used3To confirm.In addition, X-ray
The method of structure elucidation is analyzed using single crystals x-ray structure resolver (VariMax with RAPID).In 1H
In NMR and with x-ray structure parse because, only by 1H NMR analyze coordination have as symmetrical beta-diketon 1,1,1,6,
It is insufficient that three (1,1,1,6,6,6- hexafluoro -2,4- pentanediones) of 6,6- hexafluoro -2,4- pentanediones close iridium.And, these analyses
Results verification, this time manufacture complex of iridium far and away for three (1,1,1,6,6,6- hexafluoro -2,4- pentanediones) close iridium.With this
Confirm that simultaneously, the complex of iridium to reclaiming calculates yield (being calculated by iridium amount).
In the present embodiment, in addition to the test example of above-mentioned alkali process and acid treatment is carried out, also attempt based on not entering
Row alkali process and the existing method of acid treatment synthesize complex of iridium.In addition, also studied and not carrying out acid treatment and only carrying out at alkali
The situation of reason.
In the present embodiment, to iridic compound solution, carried out in each stage of alkali process, acid treatment, beta-diketon addition
PH is determined.With regard to the pH methods for measuring, pH combination electrodes (are directly read the glass electrode of temperature sensor integration and compared
The potential difference of electrode) 3 titers of pH6.86, pH4.01, pH9.18 are impregnated in, it is measured after carrying out 3 point calibrations.
Three (1,1,1,6,6,6- hexafluoro -2,4- pentanediones) on present embodiment close the result of iridium synthetic test,
PH value and yield after alkali process, acid treatment, beta-diketon addition is shown in table 1.
[table 1]
hfp:1,1,1,6,6,6- five fluoro- 2,4- pentanediones
As shown in Table 1:There is the activation process of alkali process and acid treatment by combination, three (1,1,1,6,6,6- can be synthesized
Hexafluoro -2,4- pentanediones) close iridium (1~embodiment of embodiment 8).Understand:In the activation process, in alkali process and acid treatment
All there is appropriate pH during treatment.That is, in alkali process, added by alkali, make pH for alkaline side, while being also required to make the pH be
More than 10, but not can confirm that the synthesis of complex of iridium in the comparative example 2,3 for not possessing the important document.In addition, on acid treatment, and
Solution is not only set to be transferred to acidic side, in addition it is also necessary to which it is less than more than 0.1 10 to differ from pH, in the comparative example 1 for not possessing the important document
The synthesis of complex of iridium is not can confirm that.And, the comparative example 4 for not carrying out alkali process and acid treatment or the ratio for only carrying out alkali process
Compared with the synthesis that not can confirm that complex of iridium in example 5.In addition, in not can confirm that the test example of the synthesis of these complex of iridium, molten
Change is can't see in liquid, and then, even if carrying out thin-layer chromatographic analysis (TLC) to solution, purpose thing can not be observed.
2nd implementation method:In the present embodiment, complex of iridium is manufactured by the operation of above-mentioned (2).As initiation material
Iridic compound, use iridium chloride (III) (IrCl3·nH2O), make itself and 1,1,1- tri- fluoro- 2, the 4- as beta-diketon oneself two
Reactive ketone, three (1,1,1- tri- fluoro- 2,4- acetyl butyryls) of manufacture close iridium.
[chemical formula 8]
Present embodiment is to add beta-diketon and then the method for carrying out activation process in iridic compound solution in advance.It is first
First, the iridium chloride solution obtained by addition 94mL distilled water in 10.0g iridium chlorides (iridium content 5.2g) is prepared.And, add herein
Plus the fluoro- 2,4- acetyl butyryls of 1,1,1- tri- of 25.9g, 168.1mmol.The addition is relative to iridium 1mol equivalent to 6 equivalents.In chlorination
When 1,1,1- tri- fluoro- 2,4- acetyl butyryls are added in iridium solution, apparent change is can't see in the solution, confirmation does not react.
Then, alkali process and acid treatment are carried out to the mixed solution.In the present embodiment, alkali process use the carbonic acid of 1N
Sodium solution.In addition, acid treatment uses 6% acetic acid.The method of activation process is substantially identical with the 1st implementation method.
Carry out after alkali process and acid treatment, mixed solution is heated to 55 DEG C, kept for 2.5 hours and react it.Instead
Solution after answering turns into the suspension of dark yellow.By the reacting liquid filtering and separation of solid and liquid is carried out, after cleaning solid constituent, entered
Row post is refined and three (the fluoro- 2,4- acetyl butyryls of 1,1,1- tri-) of recovery close iridium.Complex of iridium to synthesizing carries out 1H NMR analyses, nothing
Three (the fluoro- 2,4- acetyl butyryls of 1,1,1- tri-) are confirmed as doubtfully closes iridium.Afterwards, the yield of complex of iridium is calculated.
In the present embodiment, the method for not carrying out alkali process and acid treatment is studied, while to only carrying out acid
The situation for the treatment of is studied.Three (the fluoro- 2,4- acetyl butyryls of 1,1,1- tri-) on present embodiment close iridium synthetic test
Result, by alkali process, acid treatment, beta-diketon addition after pH value, yield be together shown in table 2.In addition, in present embodiment
PH methods for measuring, the method for 1H NMR in each stage are set to identical with the 1st implementation method.
[table 2]
tfh:1,1,1- tri- fluoro- 2,4- acetyl butyryls
Can confirm that:Even if in iridic compound solution before the reaction add beta diketone class, it is also possible to by activation process come
Synthesis complex of iridium (9~embodiment of embodiment 16).And understand:On in alkali process, the necessity of acid treatment and each treatment
Preferred pH scopes and pH it is poor, there is also tendency in a same manner as in the first embodiment.In addition, in the present embodiment, also attempting
The method of acid treatment is only carried out, but is unable to synthetic compound (comparative example 10).
3rd implementation method:In the present embodiment, in the present embodiment, iridium is manufactured by the operation of above-mentioned (3) to coordinate
Thing.As the iridic compound of initiation material, six ammonium chloroiridates (III) ((NH is used4)3[IrCl6]), make its with as beta-diketon
1,1,1- tri- fluoro- 2,4- pentanediones (1,1,1- trifluoroacetylacetone (TFA)) reaction, manufacture three (1,1,1- tri- fluoro- 2,4- pentanediones)
Close iridium (three (1,1,1- trifluoroacetylacetone (TFA)s) close iridium).
[chemical formula 9]
In this embodiment, in chlordene iridium acid ammonium solution, 1,1,1- tri- fluoro- 2,4- is added after alkali process have been carried out
Pentanedione, followed by acid treatment.
First, prepare the addition 470mL distilled water in the ammonium chloroiridates of 10.05g six (iridium content 4.06g, 21.1mmol) and
The chlordene iridium acid ammonium solution for obtaining.Afterwards, alkali process are carried out to the chlordene iridium acid ammonium solution.The potassium hydroxide of 1N is added in alkali process
Solution.After alkali addition, chlordene iridium acid ammonium solution is stood 1 hour at room temperature.
The fluoro- 2,4- of 1,1,1- tri- of 25.9g, 168.1mmol are added in the chlordene iridium acid ammonium solution for carried out alkali process
Pentanedione.The addition is relative to iridium 1mol equivalent to 6 equivalents.
Afterwards, acid treatment is carried out to the solution.6% phosphoric acid is used in acid treatment.The pH carried out by acid treatment is adjusted and is,
By chlordene iridium acid ammonium solution and 1, the mixed solution of 1,1- tri- fluoro- 2,4- pentanedionates is set to the solution before adjustment, is with its pH
Benchmark becomes the value of acidic side.After acid treatment, solution is heated to 55 DEG C and holding is reacted for 2.5 hours.
Reacted reaction solution turns into the suspension of dark yellow.By the reacting liquid filtering and separation of solid and liquid is carried out, cleaning is solid
After body composition, the refined (solvent of post is carried out;Hexane:Ethyl acetate=5:1) three (the fluoro- 2,4- pentanediones of 1,1,1- tri-) are reclaimed
Close iridium.To the complex of iridium for synthesizing, it is analyzed by 1HNMR, three (1,1,1- tri- fluoro- 2,4- pentanediones) is confirmed as far and away
Close iridium.Afterwards, yield is calculated.
In the present embodiment, also the method for not carrying out alkali process and acid treatment, the situation that only carries out acid treatment are carried out
Research.Three (1,1,1- tri- fluoro- 2,4- pentanediones) on present embodiment close the result of iridium synthetic test, at alkali
PH value, yield after reason, acid treatment, beta-diketon addition are together shown in table 3.In addition, the pH in each stage in present embodiment
Method for measuring, the method for 1H NMR are set to identical with the 1st implementation method.
[table 3]
tfp:1,1,1- tri- fluoro- 2,4- pentanediones
Can confirm that:Even if between alkali process and acid treatment, i.e. activation process midway addition beta-diketon in the case of,
Can also complete activation process by carrying out acid treatment to synthesize complex of iridium (17~embodiment of embodiment 24).On the party
Method, also confirms can be differed from by the pH scopes in alkali process, acid treatment, pH that learn could synthetic compound.
Industrial applicibility
As described above, according to the present invention it is possible to make broad category of beta-diketon be coordinated in iridium.Side of the invention
Method is useful as the manufacture method of the starting compound of the chemical vapor depositions such as CVD or ALD, in addition, as organic EL
The manufacture method of the raw material (intermediate raw material) of the phosphor materials of organic illuminating element such as element, organic ECL elements is also useful
's.The present invention is useful as the means that three (beta-diketons) expanded in various uses close iridium manufacturing feasibility.
Claims (6)
1. one kind three (beta-diketon) closes the manufacture method of iridium, and it is by making the beta-diketon shown in chemical formula 1 and iridic compound anti-
Answer and manufacture the beta-diketon and be coordinated in the method that three (beta-diketons) shown in the chemical formula 2 of iridium close iridium, it is characterised in that
The activation process comprising following (a) alkali process and (b) acid treatment is carried out to the iridic compound and iridic compound is lived
After change, then reacted with beta-diketon,
(a) alkali process:Alkali is added in the solution of the iridic compound, the pH of solution is in a ratio of before being added with alkali more alkaline
Side, and make the treatment that pH is more than 10;
(b) acid treatment:Acid is added in the solution for carried out the alkali process, the pH of solution is in a ratio of before being added with acid
More acidic side, and the pH of the solution before and after acid addition is differed from the treatment for turning into less than more than 0.1 10,
[chemical formula 1]
In formula, RaAnd RbFor the substitution base that the hydrogen atom of alkyl or alkyl is replaced by halogen atom;RaAnd RbIt can be different substitutions
Base, or identical replaces base;RcIt is the substitution base being made up of any one of hydrogen atom, halogen atom, alkyl,
[chemical formula 2]
R in formulaa、Rb、RcMeaning it is identical with chemical formula 1.
2. three (beta-diketons) according to claim 1 close the manufacture method of iridium, wherein, by the alkali addition in alkali process (a)
PH afterwards is set to more than 12.
3. three (beta-diketons) according to claim 1 and 2 close the manufacture method of iridium, wherein, the alkali in alkali process (a) is added
Plus the pH differences of front and rear solution are set to less than more than 2 13.
4. three (beta-diketons) according to any one of claim 1 to 3 close the manufacture method of iridium, wherein, by acid treatment (b)
In acid addition before and after solution pH difference be set to less than more than 1 10.
5. a kind of three (beta-diketons) by any one of Claims 1-4 close the manufacture method manufacture chemical vapor deposition of iridium
The method of starting compound.
6. a kind of three (beta-diketons) by any one of Claims 1-4 close the manufacture method manufacture organic light emission of iridium
The method of the intermediate raw material of element phosphor material.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014191385A JP5913501B2 (en) | 2014-09-19 | 2014-09-19 | Method for producing iridium complex |
JP2014-191385 | 2014-09-19 | ||
PCT/JP2015/074374 WO2016043016A1 (en) | 2014-09-19 | 2015-08-28 | Iridium complex production method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106715376A true CN106715376A (en) | 2017-05-24 |
CN106715376B CN106715376B (en) | 2021-12-03 |
Family
ID=55533057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580050429.4A Active CN106715376B (en) | 2014-09-19 | 2015-08-28 | Method for producing iridium complex |
Country Status (6)
Country | Link |
---|---|
US (1) | US10125158B2 (en) |
EP (1) | EP3196184B1 (en) |
JP (1) | JP5913501B2 (en) |
CN (1) | CN106715376B (en) |
TW (1) | TWI599569B (en) |
WO (1) | WO2016043016A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210047354A1 (en) * | 2019-08-16 | 2021-02-18 | Universal Display Corporation | Organic electroluminescent materials and devices |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003321415A (en) * | 2002-04-26 | 2003-11-11 | Asahi Denka Kogyo Kk | Tris(octane-2,4-dionato)iridium, raw material for chemical vapor growth comprising the same and method for producing thin film |
CN1455016A (en) * | 2002-05-01 | 2003-11-12 | 田中贵金属工业株式会社 | Raw-material compound for CVD and chemical gas-phase steam-plating method for iridium and iridium compound film |
CN1656195A (en) * | 2002-05-25 | 2005-08-17 | 科文有机半导体有限公司 | Method for producing highly pure tris-ortho metalated organoiridium compounds |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3021284B2 (en) * | 1994-05-20 | 2000-03-15 | 田中貴金属工業株式会社 | Method for producing tris (acetylacetonato) iridium (III) |
JP4856825B2 (en) * | 2001-08-23 | 2012-01-18 | 田中貴金属工業株式会社 | Raw material compound for CVD, method for producing the same, and chemical vapor deposition method of iridium or iridium compound thin film |
KR101050929B1 (en) * | 2005-09-12 | 2011-07-20 | 신닛테츠가가쿠 가부시키가이샤 | Method for producing orthometalated iridium complex of homoligand |
JP5692805B2 (en) | 2010-05-24 | 2015-04-01 | 独立行政法人産業技術総合研究所 | Method for producing iridium complex and light emitting material comprising produced iridium complex |
-
2014
- 2014-09-19 JP JP2014191385A patent/JP5913501B2/en active Active
-
2015
- 2015-08-28 US US15/503,822 patent/US10125158B2/en active Active
- 2015-08-28 WO PCT/JP2015/074374 patent/WO2016043016A1/en active Application Filing
- 2015-08-28 CN CN201580050429.4A patent/CN106715376B/en active Active
- 2015-08-28 EP EP15842524.9A patent/EP3196184B1/en active Active
- 2015-09-14 TW TW104130301A patent/TWI599569B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003321415A (en) * | 2002-04-26 | 2003-11-11 | Asahi Denka Kogyo Kk | Tris(octane-2,4-dionato)iridium, raw material for chemical vapor growth comprising the same and method for producing thin film |
CN1455016A (en) * | 2002-05-01 | 2003-11-12 | 田中贵金属工业株式会社 | Raw-material compound for CVD and chemical gas-phase steam-plating method for iridium and iridium compound film |
CN1656195A (en) * | 2002-05-25 | 2005-08-17 | 科文有机半导体有限公司 | Method for producing highly pure tris-ortho metalated organoiridium compounds |
Also Published As
Publication number | Publication date |
---|---|
TWI599569B (en) | 2017-09-21 |
CN106715376B (en) | 2021-12-03 |
US20170253623A1 (en) | 2017-09-07 |
JP2016060727A (en) | 2016-04-25 |
EP3196184A1 (en) | 2017-07-26 |
US10125158B2 (en) | 2018-11-13 |
TW201627317A (en) | 2016-08-01 |
JP5913501B2 (en) | 2016-04-27 |
EP3196184A4 (en) | 2018-05-02 |
WO2016043016A1 (en) | 2016-03-24 |
EP3196184B1 (en) | 2021-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Huynh | The organometallic chemistry of N-heterocyclic carbenes | |
Cole et al. | Synthesis and characterization of thermally robust amidinato group 13 hydride complexes | |
Mironov et al. | New mixed-ligand cyanohydroxo octahedral cluster complex trans-[Re 6 S 8 (CN) 2 (OH) 4] 4−, its luminescence properties and chemical reactivity | |
Thummel et al. | Polyaza cavity shaped molecules. 11. Ruthenium complexes of annelated 2, 2'-biquinoline and 2, 2'-bi-1, 8-naphthyridine | |
Black et al. | Organomercury Compounds. XXXI. Preparations and 199Hg NMR Spectra of Organomercury Derivatives of 2-Phenylpyridine, Benzo [h] quinoline, 1-Phenylpyrazole and 3, 4, 5-Trimethyl-1-phenylpyrazole, and the X-Ray Crystal Structure of Bis [2-(pyridin-2'-yl) phenyl] mercury | |
Zucca et al. | Rollover Cyclometalation as a Valuable Tool for Regioselective C–H Bond Activation and Functionalization | |
Coe et al. | Control of axial ligand substitution in trans-bis (2, 2'-bipyridine) ruthenium (II) complexes. Crystal and molecular structure of trans-(4-ethylpyridine)(dimethyl sulfoxide) bis (2, 2'-bipyridine) ruthenium (II) hexafluorophosphate, trans-[Ru (bpy) 2 (4-Etpy)(DMSO)](PF6) 2 | |
US20030032808A1 (en) | Tri-and bidentate amido ligands prepared by palladium0 coupling and metallation threreof to form metal-amido catalysts | |
Segl’a et al. | Metal (II)-promoted hydrolysis of pyridine-2-carbonitrile to pyridine-2-carboxylic acid. The structure of [Cu (pyridine-2-carboxylate) 2]· 2H2O | |
Zhao et al. | From osmium hydrido vinylidene to osmacycles: the key role of osmabutadiene intermediates | |
Yakhvarov et al. | A Snapshot of P4 Tetrahedron Opening: Rh‐and Ir‐Mediated Activation of White Phosphorus | |
Lazarowych et al. | Spectroscopic and chemical properties of nitrogen-15-enriched molybdenum dinitrogen complexes trans, mer-Mo (N2) 2 (L)(PMePh2) 3 | |
Luzyanin et al. | First example of an imine addition to coordinated isonitrile | |
Streubel et al. | 1, 1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations | |
CN106715376A (en) | Method of producing iridium complex | |
Mehrotra et al. | Benzimidazolines Convert Sulfur Dioxide to Bisulfate at Room Temperature and Atmospheric Pressure Utilizing Aerial Oxygen | |
Su et al. | Cycloruthenated complexes: pH-dependent reversible cyclometallation and reactions with nitrite at octahedral ruthenium centers | |
Adams et al. | Cluster synthesis. 36. New platinum-ruthenium and platinum-osmium carbonyl cluster complexes from the reactions of the complexes Pt2M4 (CO) 18 (M= ruthenium, osmium) with cycloocta-1, 5-diene in the presence of UV irradiation | |
Delgado et al. | Synthesis and structural characterization of copper (II) bishexafluoroacetylacetonate complexes with N-donor ligands | |
Funaioli et al. | Ligand-interchange reactions between M (iv)(M= Ti, V) oxide bis-acetylacetonates and halides of high-valent group 4 and 5 metals. A synthetic and electrochemical study | |
Herberhold et al. | The synthesis of thionitrosodimethylamine (Me2NN S) complexes of ruthenium, osmium, and iridium | |
Recatalá et al. | Dithiolene dimetallic molybdenum (V) complexes displaying intraligand charge transfer (ILCT) emission | |
Fuge et al. | Bridge cleavage reactions of cyclopalladated nitrosamines with thioamides and related compounds | |
Leeaphon et al. | Reactions of the polyhydride complex ReH7 (PPh3) 2 with hydroxypyridine and mercaptopyridine ligands. Formation of hydrido complexes of rhenium (III), rhenium (IV), and rhenium (V) and the characterization of eight-coordinate isomers in the solid state and in solution | |
Galardon et al. | Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS−) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |